Adhesion-promoting agent for a thermal insulation surface

ABSTRACT

The present invention relates to a novel agent for promoting adhesion to a heat-insulating surface and in particular to a polystyrene surface, especially when wet or under the effect of a large variation in temperature. The invention also relates to the use of the said agent in a water-insoluble film-forming polymer composition or in a mineral binder composition for applications in the construction field and more particularly in external heat-insulation systems.

RELATED APPLICATION DATA

This application is a continuation of U.S. patent application Ser.10/579,124 filed May 2, 2007, which claims the benefit of PCT/FR04/03082with an international filing date of Dec. 1, 2004, the entire contentsof both of which are hereby fully incorporated by reference.

The present invention relates to a novel agent for promoting adhesion toa heat-insulating surface and in particular to a polystyrene surface,especially when wet or under the effect of a large variation intemperature. The invention also relates to the use of the said agent ina water-insoluble film-forming polymer composition or in a mineralbinder composition for applications in the construction field and moreparticularly in external heat-insulation systems.

In general, polystyrene-based materials are increasingly incorporated inthe construction of new buildings, in particular in Europe.

For example, covering components made of insulating material, forinstance polystyrene such as extruded or expanded polystyrene orpolyurethane constitute a support material for laying ceramic tiles in athin-bed process.

In addition, building components made of polystyrene materials aresuitable for interrupting thermal bridges, such as those appearing, forexample, where concrete or masonry meet.

The application of panels of polystyrene-based materials to buildingfaçades, for the purpose of heat insulation, is also used.

One common method consists, in the case of heat insulation, in fixingonto the facade (for example made of masonry, concrete, mineralrendering, etc.) the back of the polystyrene insulating panels oranother insulating material made of mineral wool using a mortar or acement. A mortar is also applied to the front face of the polystyreneinsulating panels or another insulating material made of mineral wool,as a reinforcing rendering. This serves especially for the inclusion offibre reinforcements (for example reinforcements made of glass fibre,polyester or polypropylene), which are used to reinforce the mechanicalproperties of the external heat-insulating system. Next, a reinforcingrendering is usually applied again to the glass fibre trellis, for thetotal inclusion of the trellis, the surface is evened out and, afterdrying, a finish covering is applied, for example a mineral rendering ora covering based on synthetic resin, such as a roughcast, or a paint.

In general, according to the foregoing, there is an increasing problemof obtaining a permanent adhesive bond between materials based oninsulators and in particular based on polystyrene, and mineral buildingmaterials. In particular, this adhesion should be satisfactory evenunder the effect of humidity or of a large variation in temperature.

The drawback of the known mineral building materials is that theiradhesion to heat-insulating materials and in particular topolystyrene-based materials, after consolidation, is unsatisfactory.

Document EP 0 698 586 has disclosed the possibility of using an additivebased on aromatic polyether to improve the adhesion of mineral buildingmaterials to polystyrene-based materials. However, these compounds havethe drawback especially of not sufficiently improving the wet adhesionand of not sufficiently reducing the water uptake by capillary action.

One of the aims of the present invention is to provide mineral buildingmaterials that show, after consolidation, increased adhesion, when wetor under the effect of a large variation in temperature, toheat-insulating materials and in particular to polystyrene-basedmaterials.

This aim and others are achieved by the present invention, one subjectof which is a novel agent for promoting adhesion to a heat-insulatingsurface and in particular to a polystyrene surface, especially when wetor under the effect of a large variation in temperature, based on aphosphate monoester, diester or triester or a mixture thereof.

A subject of the invention is also a water-insoluble film-formingpolymer composition comprising a phosphate monoester, diester ortriester or a mixture thereof.

A subject of the invention is also the use of a water-insolublefilm-forming polymer composition comprising a phosphate monoester,diester or triester or a mixture thereof, as adhesion primer on aheat-insulating support and in particular a polystyrene-based support.

A subject of the invention is also a mineral binder compositioncomprising a phosphate monoester, diester or triester or a mixturethereof.

A subject of the invention is also the use of the mineral bindercomposition to increase the adhesion of a heat insulator and inparticular of polystyrene to a support material.

A subject of the invention is also a process for increasing the adhesionproperties to a heat-insulating support and in particular a polystyrenesupport, especially when wet or under the effect of a large variation intemperature, after consolidation, of a hydraulic mineral bindercomposition, characterized in that a sufficient amount of at least onephosphate monoester, diester or triester or a mixture thereof is addedto the said composition.

A first subject of the invention is thus a novel agent for promoting theadhesion to a heat-insulating surface and in particular a polystyrenesurface, especially when wet or under the effect of a large variation intemperature, based on a phosphate monoester, diester or triester or amixture thereof.

The term “heat-insulating support” especially means polystyrene,polyurethane and mineral wools such as glass wool or rock wool.Polystyrene is preferred.

The phosphate monoesters, diesters or triesters of the invention may bein particular compounds corresponding to formula (I) below:

O═P(OR1)(OR2)(OR3)   (I)

in which:

-   R1, R2 and R3, which may be identical or different, represent:    -   a hydrogen atom, or    -   a linear, branched or cyclic, saturated or unsaturated alkyl        radical containing from 1 to 22 carbon atoms, preferably from 2        to 12 carbon atoms and even more preferentially from 2 to 8        carbon atoms, optionally substituted with halogen atoms, such as        fluorine or chlorine, hydroxyl groups, ether groups containing        between 1 and 12 carbon atoms and preferably between 1 and 6        carbon atoms, thioether groups, ester groups, amide groups,        carboxyl groups, sulfonic acid groups, carboxylic anhydride        groups and/or carbonyl groups, or    -   an aryl radical containing from 6 to 22 carbon atoms and        preferably from 6 to 8 carbon atoms, optionally substituted with        halogen atoms, such as fluorine or chlorine, hydroxyl groups,        ether groups containing between 1 and 12 carbon atoms and        preferably between 1 and 6 carbon atoms, thioether groups, ester        groups, amide groups, carboxyl groups, sulfonic acid groups,        carboxylic anhydride groups and/or carbonyl groups,        it being understood that at least one of the substituents R1, R2        or R3 is other than a hydrogen atom.

Among the phosphate monoester, diester or triester compounds of formula(I), mention may be made of the following compounds:

-   -   tris(2-ethylhexyl)phosphate,    -   tris(2-butoxyethyl)phosphate,    -   di(2-ethylhexyl)phosphate,    -   mono(2-ethylhexyl)phosphate,    -   tris(2-isooctyl)phosphate,    -   tricresyl phosphate,    -   cresyl diphenyl phosphate,    -   trixylyl phosphate    -   triphenyl phosphate,    -   tributyl phosphate,    -   triethyl phosphate,    -   tris(2-chloroethyl)phosphate,        or a mixture thereof.

The phosphate monoester, diester or triester of the agent according tothe invention may be incorporated in liquid form or in the form of asolid powder in a water-insoluble film-forming polymer composition or ina mineral binder composition.

If the phosphate monoester, diester or triester of the invention is inliquid form at room temperature, as is the case for the particularcompounds listed above with the exception of triphenyl phosphate, whichis solid at room temperature, it is possible to adsorb them onto aninert mineral support to obtain a solid powder.

The adsorption of the phosphate monoester, diester or triester may beperformed via any conventional process for the adsorption of compoundsonto inorganic mineral supports. Mention may be made especially of theprocesses described in documents FR 74 27893 or FR 74 36083.

One preferred embodiment for preparing the solid phosphate monoester,diester or triester powder is a process comprising a step of dryimpregnation of a mineral oxide with a sufficient amount of phosphatemonoester, diester or triester.

The mineral oxide may be chosen from silica, alumina, silica-alumina,sodium silicoaluminate, calcium silicate, magnesium silicate, zirconia,magnesium oxide, calcium oxide, cerium oxide and titanium oxide. Themineral oxide may be partially or totally hydroxylated or carbonated.

The mineral oxide should have a large porosity. This means that itstotal pore volume should be at least 1 ml/g and preferably at least 2ml/g.

The total pore volume of the mineral oxide is measured via a mercuryporosimetry method using a Micromeritics Autopore III 9420 porosimeter.

The preparation of each sample is performed as follows: the sample ispredried for 2 hours in an oven at 200° C. The measurements are thentaken according to the procedure described in the manual supplied by themanufacturer.

The pore diameters are calculated by means of the Washburn relationshipwith a head contact angle equal to 140° and a gamma surface tensionequal to 485 dynes/cm.

Preferably, the mineral oxide has a working pore volume of greater thanor equal to 0.5 ml/g. The term “working volume” means the volume of thepores with a diameter of less than 1 micron. This volume is measured viathe same method as the total pore volume.

A silica is preferably used as mineral oxide. Even more preferentially,an amorphous silica is used. This may be a natural silica or a syntheticsilica, for instance silica gels, combustion silicas or, verypreferably, precipitated silicas.

When the mineral oxide is precipitated silica, it may be, for example, aTixosil 38A, Tixosil 38D or Tixosil 365 silica from the company Rhodia.

In particular, the precipitated silica may be in the form ofsubstantially spherical beads, especially with a mean size of at least80 microns, for example of at least 150 microns, obtained using a nozzlesprayer, as described, for example, in document EP 0018866. It may be,for example, the silica known as Microperle. This form makes it possibleto optimize the impregnation capacity and the flowability of the powder,as described, for example, in document EP 0 966 207 or EP 0 984 772. Itmay be, for example, a Tixosil 38X or Tixosil 68 silica from the companyRhodia.

This makes it possible especially to obtain a phosphate monoester,diester or triester powder that flows well and does not produce dust.

The precipitated silica may be a highly dispersible silica, for instancethe silicas described in documents EP 0 520 862, WO 95/09127 or WO95/09128, which, in particular, facilitates its dispersion in thewater-insoluble film-forming polymer composition or in the mineralbinder composition. It may be, for example, a Z1165 MP or Z1115 MPsilica from the company Rhodia.

The amorphous silica may be a silica with a low water uptake. The “wateruptake” corresponds to the amount of water incorporated into the samplerelative to the dry mass of the sample, after 24 hours at 20° C. and 70%relative humidity. The term “low water uptake” means a water uptake ofless than 6% and preferably less than 3%. These may be the precipitatedsilicas described in patent application FR 01 16881 (in the name of thecompany Rhodia), pyrogenic silicas or silicas that have been partiallydehydroxylated by calcinations or by surface treatment.

A subject of the invention is also a water-insoluble film-formingpolymer composition comprising a phosphate monoester, diester ortriester or a mixture thereof.

This composition may be in the form of an aqueous dispersion ofwater-insoluble film-forming polymer (latex) or in the form of aredispersible latex powder. The term “redispersible latex powder” meansa latex powder that is redispersible in water.

The process for preparing this composition consists in mixing aphosphate monoester, diester or triester or a mixture thereof with awater-insoluble film-forming polymer (latex).

This mixture of the phosphate monoester, diester or triester and of thelatex may be prepared in the form of a mixture of solid phosphatemonoester, diester or triester powder with a redispersible latex powdercomposition.

It is also possible to introduce the phosphate monoester, diester ortriester into the latex during the polymerization or afterpolymerization. The supplemented latex in the form of an aqueousdispersion may thus be obtained.

Drying of the aqueous dispersion thus obtained may also be performed inorder to obtain a redispersible latex powder supplemented with phosphatemonoester, diester or triester.

It is also possible to add the phosphate monoester, diester or triesterin powder form to the spraying tower of the latex, i.e. at the time ofdrying of the latex.

Among all these possible forms of mixtures, the case in which thephosphate monoester, diester or triester is introduced into an aqueousdispersion of film-forming polymer (latex) after polymerization ispreferred. The latex may then be dried.

The amount of phosphate monoester, diester or triester added to thewater-insoluble film-forming polymer should be sufficient to give thewater-insoluble film-forming polymer composition good properties ofadhesion to polystyrene, even when wet.

The amount of phosphate monoester, diester or triester added to thewater-insoluble film-forming polymer is then generally between 0.02% and25% by weight of phosphate monoester, diester or triester relative tothe weight of the dry latex.

This amount is preferably between 0.5% and 8% by weight of phosphatemonoester, diester or triester relative to the weight of the dry latex.

Even more preferentially, this amount is between 1% and 5% by weight ofphosphate monoester, diester or triester relative to the weight of thedry latex.

Water-insoluble polymers that are particularly suitable are homopolymersor copolymers in the form of an aqueous dispersion or that may beconverted into an aqueous dispersion, and can then be converted intopowder by spray-drying.

The mean particle size of the powder is preferably from 10 to 1000 μm,more preferably from 20 to 700 μm and particularly from 50 to 500 μm.

The preferred water-insoluble polymers are obtained by polymerization ofmonomers chosen from:

-   -   vinyl esters and more particularly vinyl acetate;    -   alkyl acrylates and methacrylates, the alkyl group of which        contains from 1 to 10 carbon atoms, for example methyl, ethyl,        n-butyl or 2-ethylhexyl acrylate or methacrylate;    -   vinylaromatic monomers, in particular styrene.

These monomers may be copolymerized together or with other ethylenicallyunsaturated monomers, to form homopolymers, copolymers or terpolymers.

As non-limiting examples of monomers that are copolymerizable with vinylacetate and/or acrylic esters and/or styrene, mention may be made ofethylene and olefins, for instance isobutene or α-olefins containingfrom 6 to 20 carbon atoms and preferably from 8 to 14 carbon atoms;vinyl esters of branched or unbranched saturated monocarboxylic acidscontaining from 1 to 16 carbon atoms, for instance vinyl propionate,vinyl “Versatate” (registered brand name for branched C₉-C₁₁ acidesters) and in particular for the vinyl neodecanoate known as Veova 10,vinyl pivalate, vinyl butyrate, vinyl 2-ethylhexylhexanoate or vinyllaurate; esters of unsaturated monocarboxylic or dicarboxylic acidscontaining from 3 to 6 carbon atoms with alkanols containing 1 to 10carbon atoms, for instance methyl, ethyl, butyl or ethylhexyl maleate orfumarate; vinylaromatic monomers such as methylstyrenes andvinyltoluenes; vinyl halides such as vinyl chloride or vinylidenechloride; diolefins, particularly butadiene; (meth)allylic esters of(meth)acrylic acid, (meth)allylic esters of maleic, fumaric, crotonicand itaconic acid monoesters and diesters, and also alkene derivativesof acrylic and methacrylic acid amides, such as N-methallylmaleimide.

It is especially possible to choose at least 2 copolymerizable monomersof different nature to obtain a terpolymer.

An example that may be mentioned is a terpolymer of vinyl acetate/vinylversatate/dibutyl maleate type.

It is also possible to add to the monomers that are copolymerizable withvinyl acetate and/or acrylic esters and/or styrene at least one othermonomer chosen from the following list:

-   -   acrylamide, ethylenically unsaturated carboxylic acids or        diacids, preferably acrylic acid, methacrylic acid or crotonic        acid, ethylenically unsaturated sulfonic acids and salts        thereof, preferably vinylsulfonic acid or        2-acrylamido-2-methylpropanesulfonic (AMPS) acid, or sodium        methallylsulfonate;    -   crosslinking monomers bearing at least two ethylenic        unsaturations, such as diallyl phthalate, diallyl maleate, allyl        methacrylate, triallyl cyanurate, divinyl adipate or ethylene        glycol dimethacrylate;    -   monomers with silane functions such as vinyltrimethoxysilane or        vinyltriethoxysilane.

These monomers are added in an amount generally of between 0.05% and10.0% by weight relative to the total weight of the monomers. Thesemonomers are added during the polymerization.

Generally, the polymerization of the monomers is performed in anemulsion polymerization process in the presence of an emulsifier and/orof a protective colloid, and of a polymerization initiator.

The monomers used may be introduced as a mixture or separately andsimultaneously into the reaction medium, either before the start of thepolymerization in one go, or during the polymerization in successivefractions or continuously.

The emulsifiers that may be used are anionic, cationic or nonionicemulsifiers.

They are generally used in a proportion of from 0.01% to 5% by weightrelative to the total weight of the monomers.

Emulsifiers generally used include standard anionic agents representedespecially by alkyl sulfates, alkyl sulfonates, alkylaryl sulfates,alkylaryl sulfonates, aryl sulfates, aryl sulfonates, sulfosuccinates,alkali metal alkyl phosphates, and salts of hydrogenated ornon-hydrogenated abietic acid.

The emulsion polymerization initiator is more particularly representedby hydroperoxides such as hydrogen peroxide, cumene hydroperoxide,diisopropylbenzene hydroperoxide, para-menthane hydroperoxide ortert-butyl hydroperoxide, and persulfates such as sodium persulfate,potassium persulfate or ammonium persulfate. It is used in an amountgenerally of between 0.05% and 3% by weight relative to the total weightof the monomers. These initiators are optionally combined with areducing agent, such as sodium bisulfite, hydrogen sulfite orthiosulfate, sodium formaldehydesulfoxylate, polyethyleneamines, sugars(dextrose or saccharose), ascorbic acid or isoascorbic acid, or metalsalts. The amount of reducing agent used usually ranges from 0 to 3% byweight relative to the total weight of the monomers.

The reaction temperature, which depends on the initiator used, isgenerally between 0 and 100° C. and preferably between 30 and 90° C.

A transfer agent may be used in proportions ranging from 0 to 3% byweight relative to the monomer(s), generally chosen from mercaptans suchas N-dodecyl mercaptan, tert-dodecyl mercaptan and 2-mercaptoethanol,allylic derivatives such as allyl alcohol, cyclohexene, and halogenatedhydrocarbons such as chloroform, bromoform and carbon tetrachloride. Itallows the length of the molecular chains to be regulated. It is addedto the reaction medium either before the polymerization or duringpolymerization.

Protective colloids may also be used, at the start, during or afterpolymerization.

The protective colloids that are particularly suitable are polyvinylalcohols and derivatives thereof, for example vinyl alcohol/vinylacetate copolymers, modified polyvinyl alcohols comprising reactivefunctions such as silanols, mercaptans, amines and formamides, andcomprising hydrophobic comonomers such as ethylene, vinyl versatate,vinyl 2-ethylhexylhexanoate, polyvinylpyrrolidones (PVP),polysaccharides, for example starches (amylose and amylopectin),cellulose, cellulose ethers, for instance hydroxyethylcellulose, guar,tragacantic acid, dextran, alginates and carboxymethyl, methyl,hydroxyethyl or hydroxypropyl derivatives thereof, proteins, for examplecasein, soybean proteins, gelatines, synthetic polymers, for examplepoly(meth)acrylic acid, poly(meth)acrylamide, polyvinylsulfonic acids,and water-soluble copolymers thereof, melamine-formaldehyde sulfonates,naphthalene-formaldehyde sulfonates, styrene/maleic acid copolymers, andvinyl ether/maleic acid copolymers. Polyvinyl alcohol is particularlypreferred as protective colloid for the polymerization. A particularprotective colloid used is a polyvinyl alcohol with a degree ofpolymerization of from 200 to 3500 and a degree of hydrolysis of from 80mol % to 99 mol % and preferably from 86 mol % to 92 mol %.

The protective colloids are added in proportions of between 0.5% and 15%by weight relative to the total weight of the monomers and preferablybetween 2% and 10% by weight relative to the total weight of themonomers.

In one particularly preferred embodiment, the latex compositionsupplemented with phosphate monoester, diester or triester in the formof a redispersible powder comprises from 0 to 35% by weight andpreferably 3% to 15% by weight of protective colloid relative to thetotal weight of the water-insoluble polymer.

The protective colloids that are particularly suitable are the same asthose mentioned above.

The preferred anticaking agents are aluminium silicates, calciumcarbonates, magnesium carbonates or mixtures thereof, silicas, hydratedalumina, bentonite, talc, or mixtures of dolomite and talc, or ofcalcite and talc, kaolin, barium sulfate, titanium oxide or calciumsulfoaluminate (satin white).

The particle size of the anticaking agents is preferably between 0.001and 0.5 mm.

The water-insoluble film-forming polymer composition comprising aphosphate monoester, diester or triester or a mixture thereof may alsocomprise a water repellent chosen from fatty acids or salts thereof suchas calcium, magnesium or sodium stearate, or sodium laurate, and fattyacid esters such as those described in document WO 01/90023 (MBT).

Particular water repellents that may be mentioned include methyl estersof C10-C16 fatty acids (containing from 10 to 16 carbon atoms), forinstance those sold under the brand name Estorob 1214 by the companyNovance, the methyl ester of erucic acid, the methyl ester of linoleicacid, the ethylhexyl ester of lauric acid, the butyl ester of oleicacid, the ethylhexyl ester of oleic acid or the methyl ester of oleicacid.

Preferably, the water-insoluble film-forming polymer compositioncomprising a phosphate monoester, diester or triester or a mixturethereof comprises, as particularly advantageous water repellent, themethyl ester of a C10-C16 fatty acid.

This water-insoluble film-forming polymer composition comprising aphosphate monoester, diester or triester or a mixture thereof especiallyhas the advantage of being able to be used as such or in combinationwith other additives, for instance adhesion primer on a support made ofa heat insulator and in particular on a polystyrene support.

Thus, a subject of the invention is also the use of the water-insolublefilm-forming polymer composition comprising a phosphate monoester,diester or triester or a mixture thereof as adhesion primer on a supportmade of a heat insulator and in particular a polystyrene support.

This water-insoluble film-forming polymer composition comprising aphosphate monoester, diester or triester or a mixture thereof also hasthe advantage of reducing the glass transition temperature (Tg) and theminimum film-forming temperature (MFFT) of the non-supplementedwater-insoluble film-forming polymer (latex).

A subject of the invention is also a mineral binder compositioncomprising a phosphate monoester, diester or triester or a mixturethereof.

The mineral binders may be aerial binders or hydraulic binders. The term“aerial binder” means plaster-based binders.

The hydraulic mineral binders may be chosen from cements, which may beof Portland, aluminous or blast-furnace type. Other compounds oftenadded as additives to the cement also have hydraulic properties, forinstance fly ash and calcined shales. Mention may also be made ofpozzolans which react with lime and form calcium silicates.

The mineral binders are generally manufactured from natural materialsthat are treated at very high temperature to remove the water andconvert the materials into mineral compounds capable of reacting withwater to produce a binder, which, after drying, forms a compact masswith good mechanical properties.

The mineral binders may be in the form of grouts, mortars or concretes;thus, fine or coarser granulates, such as sand or pebbles, are thusgenerally added during the puddling with water.

The phosphate monoester, diester or triester may be added directly tothe building composition, in an amount that may be between 0.01 % and50% by dry weight of the phosphate monoester, diester or triesterrelative to the total weight of the building composition.

Preferably, this amount is between 0.05% and 20% by dry weight ofphosphate monoester, diester or triester relative to the total weight ofthe building composition.

Even more preferentially, this amount is between 0.02% and 2% by dryweight of phosphate monoester, diester or triester relative to the totalweight of the building composition.

The phosphate monoester, diester or triester may also be premixed in asufficient amount with a water-insoluble film-forming polymer in theform of an aqueous dispersion (latex) or in the form of a redispersiblelatex powder before being added to the mineral binder composition.

The binder composition thus comprises, besides the said phosphatemonoester, diester or triester, at least one water-insolublefilm-forming polymer.

The amounts of phosphate monoester, diester or triester or mixturethereof generally introduced into the water-insoluble film-formingpolymer compositions are the same as those indicated above.

The redispersible latex powder supplemented with phosphate monoester,diester or triester used may be of very varied nature.

A latex composition in the form of a redispersible powder comprising:

-   at least one water-insoluble polymer,-   from 0 to 35% by weight and in particular from 3% to 15% by weight,    relative to the total weight of the polymer, of at least one    protective colloid,-   from 0 to 30% by weight and in particular from 1% to 12% by weight,    relative to the total weight of the polymer, of an anticaking agent,    and-   from 0.02% to 25% by weight and in particular from 0.5% to 8% by    weight, relative to the total weight of the polymer, of phosphate    monoester, diester or triester,-   is particularly preferred.

The redispersible latex powder supplemented with phosphate monoester,diester or triester is preferably prepared by spray-drying the aqueouspolymer dispersion. This drying may be performed in conventionalspray-drying systems, using atomization by means of simple, twin ormultiple liquid nozzles or a rotary disc. The selected product outlettemperature is generally in the range from 50 to 100° C. and preferablyfrom 60 to 90° C., depending on the system and on the desired glasstransition temperature of the latex and the desired degree of drying.

In order to increase the stability on storage and the flowability of theredispersible latex powder, it is preferable to introduce an anticakingagent into the spraying tower together with the aqueous polymerdispersion, which results in a preferable deposition of the anticakingagent onto the particles of the dispersion.

The mineral binder composition thus obtained has, after consolidation,good properties of adhesion to heat insulators and in particular topolystyrene, especially when wet or under the effect of a largevariation in temperature.

It also has good water-repellency properties and a reduction in wateruptake by capillary action.

Besides the mineral constituents, the mineral binder compositions mayalso comprise organic additives, for example hydrocolloids such ascellulose ethers or guars, plasticizers, water repellents such as thosementioned previously in the water-insoluble film-forming polymercompositions, mineral or organic fibres such as fibres of polypropylene,polyethylene, polyamide, cellulose or crosslinked polyvinyl alcoholtype, or a mixture thereof.

The mineral binder composition may also comprise mineral or organicdyes. This is the case in particular when this mineral bindercomposition is used as a finishing coat.

The mineral binder composition may also comprise any additive usuallyused in mineral binder compositions.

The composition according to the invention, especially the mineralbinder composition according to the invention, may also comprise asilicone, preferably chosen from polyorganosiloxanes, in particularpolyorganosiloxanes that are liquid at room temperature. This siliconemay be introduced after polymerization, or in the form of powder.

A subject of the invention is also a process for increasing theproperties of adhesion to a heat insulator and in particular topolystyrene, especially when wet or under the effect of a largevariation in temperature, after consolidation, of a mineral bindercomposition, characterized in that a sufficient amount of at least onephosphate monoester, diester or triester or a mixture thereof is addedto the said composition.

A subject of the present invention is also the use of this mineralbinder composition to increase the adhesion of a heat insulator and inparticular of polystyrene to a support material.

The support materials may be composed of concrete, bricks, cellularconcrete, agglomerated concrete (breeze block), fibrocement, masonry orwall rendering.

Other advantages of the compositions or processes of the invention areindicated in the examples that follow, which are given as non-limitingillustrations.

The proportions and percentages indicated in the examples are on aweight basis, unless otherwise indicated.

The particle sizes (d50) are measured using a Coulter LS 230 laserscattering granulometer.

EXAMPLES Description of the Tests 1—Test of Adhesion to Polystyrene

Mortar is spread onto the insulator to a thickness of 3 mm 15 minutesafter puddling. After drying the mortar for 28 days (at 23±2° C. and50±5% RH (relative humidity)), eight circles 50 mm in diameter are cutout of the mortar down to the insulator, using a borer. Round metalpellets of appropriate size are attached to these areas using anaraldite adhesive.

The peel test is performed under the following conditions:

-   -   without additional conditioning (in the dry state),    -   after immersing the mortar in water for 2 days and drying for 2        hours (at 23±2° C. and 50±5% RH).

The mean peel value is based on the results of eight tests. Theindividual and mean values are recorded and the results expressed asMPa.

2—Test of Water Uptake by Capillary Action on Stone

Three ceramic tiles are prepared for each formulation.

The rendering (thickness 3 mm) is applied using a trowel to one face ofthe ceramic tile. The ceramic tile thus prepared is conditioned for 28days (at 23±2° C. and 50±5% RH). The side faces of the ceramic tile aremade waterproof so as to ensure that only the face covered with the coatof rendering is subjected to water uptake during the test.

The face covered with the ceramic tile rendering is placed in contactwith a sponge (a filter paper is placed beforehand between the ceramictile and the sponge) placed in a tank containing water.

The ceramic tiles are weighed before immersion (reference weight) andthen after 30 minutes, 1 hour, 2 hours, 4 hours, 6 hours and 24 hours.Before the second and the subsequent weighings, the surface of theceramic tiles is wiped using an absorbent paper.

The calculation is directed towards determining the mean water uptakeper square metre over time.

Example 1 Preparation of a Latex Emulsion Supplemented with a VinylAcetate/Vinyl Neodecanoate Copolymer (Sold Under the Brand Name Veova 10by the Company Resolution) and with tris(2-butoxyethyl)phosphate

A latex composed of a copolymer of vinyl acetate/vinyl versatatecomposed of 50% vinyl acetate and 50% vinyl versatate (Veova 10) byweight is used as control binder. This latex is synthesized via anemulsion polymerization process using polyvinyl alcohol with a degree ofhydrolysis of about 88% as protective colloid and potassium persulfateas free-radical initiator.

The characteristics of this latex:

Dry extract: 50.73% pH: 4.7 MFFT: 7.6° C. Tg: 16° C. Brookefieldviscosity 2420 mPa · s. at 50 rpm: Granulometry: d50: 2 μm Additive:Amgard TBEP (Rhodia) = tris(2-butoxyethyl) phosphate (CAS = 78-51-3)Physical form: liquid

Preparation of the Latex Forming the Subject of the Invention

801.7 grams of control latex are introduced into a 1-litre reactorequipped with an anchor-type stirrer. This latex is heated to atemperature of between 60 and 70° C., and 16.3 grams of Amgard TBEP areadded over a period of about 20 minutes. After the end of addition ofthe Amgard TBEP, the mixture is maintained at this temperature for afurther 20 to 30 minutes and is then cooled to room temperature.

This latex may then be formulated in its present form or may be atomizedin the presence of an anticaking agent (for example kaolin or silica) toobtain a water-redispersible powder.

Characteristics of the Latex Forming the Subject of the Invention

Content of Amgard TBEP/dry latex:    4% Dry extract: 51.91% pH: 4.7MFFT: 0° C. Tg: 7° C. Brookfield viscosity at 50 rpm: 2068 mPa · sGranulometry: d50: 2 μm

Composition of the Formulation of the Rendering Used for Bonding and thePolystyrene-Based Rendering

Grey cement CPA CEMI 42.5: 600 g Sand HN38 (0.4-4 mm) 1296 g Celluloseether Culminal 9101: 1 g Cellulose ether Culminal 9104: 3 g Lime: 40 gLatex emulsion supplemented with 115.6 g Amgard TBEP: Grey cement CPACEMI 42.5: 600 g Sand HN38 (0.4-4 mm) 1296 g Cellulose ether Culminal9101: 1 g Cellulose ether Culminal 9104: 3 g Lime: 40 g Control latexemulsion: 118.3 g Water/powder ratio = 0.22

Physicochemical Properties of the Control and Supplemented Emulsions

TABLE 1 Reference Viscosity Tg MFFT Control latex 2436 mPa · s 16° C.7.6° C. Control latex supplemented 2068 mPa · s  7° C.   0° C. withAmgard TBEP (4%)

The addition of the phosphate ester is reflected by a plasticizingeffect on the polymer, with a consequent large drop in its Tg (glasstransition temperature) and in its MFFT (minimum film-formingtemperature).

Test of Adhesion to Polystyrene of the Supplemented Control Latex

The results of the test of adhesion to polystyrene of the control latexsupplemented with Amgard TBEP are given in Table 2.

TABLE 2 Adhesion 28 days Adhesion 28 days + 2 days Reference (N/mm²) inwater (N/mm²) Control emulsion 0.012 0.045 Control emulsion 0.012 0.063supplemented with Amgard TBEP

The mortar containing the control latex supplemented with Amgard TBEPhas an adhesion to polystyrene (0.065 N/mm²) after immersion in waterfor 2 days and drying for 2 hours (at 23° C.±2° C.) higher than themortar containing the non-supplemented control latex (0.045 N/mm²).

Test of Water Uptake by Capillary Action on Stone of the SupplementedControl Latex

The results of the test of water uptake by capillary action on stone ofthe control latex supplemented with Amgard TBEP are presented in Table3.

TABLE 3 Control emulsion supplemented Control emulsion with Amgard TBEPTime h^(1/2) Water absorption (kg/m²) Water absorption (kg/m²) 0.7 0.310.54 1 0.43 0.73 1.41 0.87 1.18 2 5.41 2.46 2.45 9.95 3.52 4.9 18.0510.37

The amount of water adsorbed by capillary action measured after 24 hoursis less in the case where the mortar contains the control latexsupplemented with Amgard TBEP (7.1 kg/m²) compared with the mortarcontaining the control latex (18.3 kg/m²).

Example 2

Amgard TOF=tris(2-ethylhexyl)phosphate (CAS 1806-54-8) sold by thecompany Rhodia.

Amgard TBEP=tris(2-butoxyethyl)phosphate (CAS 78-51-3) sold by thecompany Rhodia.

Physical form: liquid

Preparation of Latex Powders Forming the Subject of the Invention

A latex composed of a vinyl acetate/vinyl versatate copolymer with aweight composition of 50% vinyl acetate and 50% vinyl versatate (Veova10) is used as control binder. This latex is synthesized via an emulsionpolymerization process using polyvinyl alcohol with a degree ofhydrolysis of about 88% as protective colloid and potassium persulfateas radical initiator. The characteristics of this latex are:

Dry extract: 50.0% pH: 4.8 MFFT: 7.5° C. Tg: 15.5° C. Brookfieldviscosity at 50 rpm: 3000 mPa · s Granulometry: d50: 1.9 μm

11 kg of control latex are introduced into a 25-litre reactor equippedwith an anchor-type stirrer. This latex is heated to a temperature ofbetween 60 and 70° C., and 220 grams of Amgard TBEP or Amgard TOF areadded over a period of about 20 minutes. After the end of addition ofthe Amgard, the mixture is maintained at this temperature for a further20 to 30 minutes and is then cooled to room temperature.

The drying of the suspension was performed via a Niro-type atomizationprocess. The attack air temperature is between 110 and 160° C. andpreferably, herein, between 120 and 150° C., and the outlet temperatureis between 50 and 90° C. and preferably, herein, between 60 and 80° C.The spraying of the polymer suspension is performed in the presence ofmineral or organic fillers that improve the flowability of the productand prevent caking. These fillers may be, for example, carbonates,silicates, silica, double salts (talc or kaolin) or mixtures of thesevarious fillers. The contents of these mineral fillers range from 2% to20% and preferably, herein, between 5% and 15%.

Characteristics of the Latex Powders Forming the Subject of theInvention Control Powder:

% residual humidity:   1% Mean content of mineral agent: 9.6% Meangranulometry d50: 74 μmExample of Latex Powder Supplemented with Amgard TBEP

Content of Amgard/dry latex:   4% Latex characteristics: Dry extracts:50.8% pH: 4.8 MFFT: 0° C. Brookfield viscosity at 50 rpm: 3024 mPa · sGranulometry: d50: 1.9 μm Powder characteristics: % residual humidity: 1.2% Mean content of mineral agent:   12% Mean granulometry d50: 79 μmExample of Latex Powder Supplemented with Amgard TOF

Content of Amgard/dry latex:   4% Latex characteristics: Dry extract:51.1% pH: 4.8 MFFT: 0° C. Brookfield viscosity at 50 rpm: 2968 mPa · sGranulometry: d50: 1.9 μm Powder characteristics: % residual humidity:0.83% Mean content of mineral agent:   13% Mean granulometry d50: 62 μm

Composition of the Formulation of the Rendering Used for the BondingMortar and the Base Rendering on Polystyrene

Grey cement 42.5 R: 600 g Sand HN38 (0.4-4 mm) 1295.7 g Cellulose etherCulminal 9101: 1 g Cellulose ether Culminal 9104: 3 g Lime: 40 g Latexpowder: 60 g Water/powder ratio = 0.22

Results Adhesion to Polystyrene

TABLE 4 Adhesion 28 days Adhesion 28 days + 2 days Reference (N/mm²) inwater (N/mm²) Control powder 0.09 0.015 Control powder 0.128 0.035supplemented with Amgard TBEP Control powder 0.108 0.029 supplementedwith Amgard TOF

The adhesion measured after 28 days and after curing in water is greaterin the case of the mortars containing the control powders supplementedwith Amgard TBEP and Amgard TOF compared with the mortar containing thenon-supplemented control powder.

Water Uptake by Capillary Action on Stone

TABLE 5 Control powder Control powder supplemented with supplementedwith Control powder Amgard TBEP Amgard TOF water absorption Waterabsorption Water absorption Time h^(1/2) (kg/m²) (kg/m²) (kg/m²) 0.71.19 0.88 0.26 1 2.31 1.59 0.42 1.41 4.04 2.93 0.80 2 9.62 5.78 1.262.45 13.02 8.04 1.66 4.9 16.45 14.22 8.17

The amounts of water absorbed are less in the case of the mortarscontaining the control powders supplemented with Amgard TBEP and AmgardTOF compared with the mortar containing the non-supplemented controlpowder.

Example 3 Emulsion of Terpo+Additives

Estorob 1214: methyl ester of C10-C16 acid (CAS=66762-40-7) sold by thecompany Novance

Montasolve CLP: cresol propoxylated with about 6 units of propyleneoxide (CAS=9064-13-5) sold by the company SEPPIC

Preparation of the Latex Forming the Subject of the Invention

A latex composed of a copolymer of vinyl acetate/vinyl versatate anddibutyl maleate having a weight composition of 50% vinyl acetate, 50%vinyl versatate (Veova 10) and 25% dibutyl maleate is used as controlbinder. This latex is synthesized via an emulsion polymerization processusing polyvinyl alcohol with a degree of hydrolysis of about 88% asprotective colloid and potassium persulfate as free-radical initiator.

The characteristics of this latex are:

Dry extract: 50.73% pH: 4.7 MFFT:  5° C. Tg: 16° C. Brookfield viscosityat 50 rpm: 2420 mPa · s Granulometry: d50: 2 μm

Characteristics of the Latex Forming the Subject of the InventionExample of Terpo Control Latex

Dry extract: 50.73% pH: 4.7 MFFT: 5° C. Brookfield viscosity at 50 rpm:2420 mPa · s Granulometry: d50: 2 μmExample of Control Latex Supplemented with Amgard TBEP

Content of Amgard/dry latex:   4% Dry extract: 52.0% pH: 4.8 MFFT: 0° C.Brookfield viscosity at 50 rpm: 1320 mPa · s Granulometry: d50: 2 μm

Comparative Example Control Latex Supplemented with Propoxylated Cresol(Montasolve CLP)

Content of propoxylated cresol/dry latex:   4% Dry extract: 51.9% pH:4.8 MFFT: 0° C. Brookfield viscosity at 50 rpm: 1390 mPa · sGranulometry: d50: 2 μmExample of Control Latex Supplemented with Amgard TBEP and Estorob 1214

Estorob 1214: CAS = 66762-40-7 sold by the company Novance Content ofAmgard/dry latex:   2% Content of Estorob 1214:   2% Dry extract: 51.9%pH: 4.8 MFFT: 0° C. Brookfield viscosity at 50 rpm: 1216 mPa · sGranulometry: d50: 2 μm

Composition of the Rendering Formulation Used for the Bonding Mortar andthe Base Rendering on the Polystyrene Example of Control Latex

Grey cement 42.5 R: 600 g Sand HN38 (0.4-4 mm) 1295.7 g Cellulose etherCulminal 9101: 1 g Cellulose ether Culminal 9104: 3 g Lime: 40 gEmulsion of control latex: 118.3 g Water/powder ratio = 0.22Example of Control Latex Supplemented with Amgard TBEP

Grey cement 42.5 R: 600 g Sand HN38 (0.4-4 mm) 1295.7 g Cellulose etherCulminal 9101: 1 g Cellulose ether Culminal 9104: 3 g Lime: 40 gEmulsion of latex supplemented with Amgard: 116.3 g Water/powder ratio =0.22

Comparative Example Control Latex Supplemented with Propoxylated Cresol(Montasolve CLP)

Grey cement 42.5 R: 600 g Sand HN38 (0.4-4 mm) 1295.7 g Cellulose etherCulminal 9101: 1 g Cellulose ether Culminal 9104: 3 g Lime: 40 gEmulsion of latex supplemented with 116.3 g propoxylated cresol:Water/powder ratio = 0.22Example of Control Latex Supplemented with Amgard TBEP and Estorob 1214

Grey cement 42.5 R: 600 g Sand HN38 (0.4-4 mm) 1295.7 g Cellulose etherCulminal 9101: 1 g Cellulose ether Culminal 9104: 3 g Lime: 40 gEmulsion of latex supplemented with 116 g Amgard TBEP and Estorob 1214:Water/powder ratio - 0.22

Results Adhesion to Polystyrene

TABLE 6 Adhesion 28 Adhesion 28 days days + 2 days Reference (N/mm²) inwater (N/mm²) Control emulsion 0.061 0.006 Control emulsion 0.104 0.027supplemented with propoxylated cresol (Montasolve CLP), comparativeexample Control emulsion 0.132 0.052 supplemented with Amgard TBEPControl emulsion 0.113 0.034 supplemented with Amgard TBEP and Estorob1214

The adhesion to polystyrene measured after 28 days and curing in waterin the case of the mortars containing the control emulsion and thecontrol emulsion supplemented with propoxylated cresol is less than thatmeasured in the case of the mortars containing the control emulsionsupplemented with Amgard TBEP and the mixture Amgard TBEP plus Estorob1214.

Water Uptake by Capillary Action on Stone

TABLE 7 Control emulsion Control emulsion Control emulsion supplementedwith supplemented with supplemented with Amgard TBEP and Controlemulsion propoxylated cresol Amgard TBEP Estorob 1214 Water absorptionWater absorption Water absorption Water absorption Time h^(1/2) (kg/m²)(kg/m²) (kg/m²) (kg/m²) 0.7 1.92 0.40 0.58 0.15 1 3.44 0.55 0.76 0.211.41 6.56 1.17 1.32 0.29 2 11.71 3.89 2.92 0.42 2.45 14.60 7.08 4.570.58 4.9 16.78 15.47 12.70 2.46

The amounts of water absorbed are less in the case of the mortarcontaining the control emulsion supplemented with the mixture of AmgardTBEP and Estorob 1214.

Example 4 Control/BEHPA Powder Mixture

BEHPA: bis(2-ethylhexyl)phosphoric acid (CAS=298-07-7) sold by thecompany Rhodia

Preparation of the Mixture

BEHPA (0.5% by weight/latex powder) is premixed with the latex powderbefore introduction into the mixture containing the various fillers.

Composition of the Rendering Formulation Used for the Bonding Mortar andthe Base Rendering on Polystyrene

Grey cement 42.5 R: 600 g Sand HN38 (0.4-4 mm) 1295.4 g Cellulose etherCulminal 9101: 1 g Cellulose ether Culminal 9104: 3 g Lime: 40 g Latexpowder: 60 g BEHPA: 0.3 g Water/powder ratio = 0.22

Results Adhesion to Polystyrene

TABLE 8 Adhesion 28 days Adhesion 28 days + 2 days Reference (N/mm²) inwater (N/mm²) Control powder 0.127 0.014 Control powder mixed 0.1430.041 with BEHPA

The adhesion to polystyrene measured after 28 days and after curing inwater is greater in the case of the mortar containing the control powdermixed with BEHPA compared with the non-supplemented control powder.

Water Uptake by Capillary Action on Stone

TABLE 9 Control powder mixed Control powder with BEHPA Time h^(1/2)Water absorption (kg/m²) Water absorption (kg/m²) 0.7 5.35 1.71 1 7.522.81 1.41 12.31 7.14 2 17.78 10.92 2.45 18.03 13.95 4.9 18.44 17.61

The amount of water absorbed is less in the case of the mortarcontaining the control powder mixed with BEHPA compared with the mortarcontaining the non-supplemented control powder.

1. An article of construction comprising a heat-insulating materialadhered to a mineral building material and an adhesion promoting agentcomprising a a phosphate monoester, diester or triester represented bythe formula:O═P(OR1)(OR2)(OR3) wherein R1, R2 and R3, may be the same or differentand are a hydrogen atom, a linear, branched or cyclic, saturated orunsaturated alkyl radical containing from 1 to 22 carbon atoms,optionally substituted with halogen atoms, hydroxyl groups, ether groupscontaining between 1 and 12 carbon atoms, thioether groups, estergroups, amide groups, carboxyl groups, sulfonic acid groups, carboxylicanhydride groups, carbonyl groups, an aryl radical containing from 6 to22 carbon atoms, optionally substituted with halogen atoms, providedhowever that at least one of R1, R2 or R3 is not a hydrogen atom.
 2. Thearticle of construction of claim 1 wherein the phosphate monoester,diester or triester of formula (I) is selected from the group consistingof tris(2-ethylhexyl)phosphate, tris(2-butoxyethyl)phosphate,di(2-ethylhexyl)phosphate, mono(2-ethylhexyl)phosphate,tris(2-isooctyl)phosphate, tricresyl phosphate, cresyl diphenylphosphate, trixylyl phosphate, triphenyl phosphate, tributyl phosphate,triethyl phosphate, tris(2-chloroethyl)phosphate, and combinationsthereof.
 3. The article of construction of claim 1 wherein the phosphatemonoester, diester or triester is adsorbed onto an inert mineral supportselected from the group consisting of silica, alumina, silica-alumina,sodium silicoaluminate, calcium silicate, magnesium silicate, zirconia,magnesium oxide, calcium oxide, cerium oxide and titanium oxide.
 4. Thearticle of construction of claim 1 wherein the adhesion promoting agentis in a water-insoluble film-forming polymer composition.
 5. The articleof construction of claim 4 wherein the water-insoluble film formingcomposition is in the form of an aqueous dispersion (latex) or is in theform of a redispersible latex powder.
 6. The article of construction ofclaim 5 wherein the phosphate monoester, diester or triester is presentin an amount between 0.02% and 25% by weight relative to the weight ofthe latex powder.
 7. The article of construction of claim 6 wherein thephosphate monoester, diester or triester is present in an amount between1% and 5% by weight relative to the weight of the latex powder.
 8. Thearticle of construction of claim 4 wherein the polymer composition isobtained by polymerization of monomers selected from the groupconsisting of vinyl esters of branched or unbranched, saturatedmonocarboxylic acids containing from 1 to 16 carbon atoms, alkylacrylates and methacrylates, the alkyl group of which contains from 1 to10 carbon atoms, vinylaromatic monomers, wherein the monomers arecopolymerized with each other or with other ethylenically unsaturated.9. The article of construction of claim 1 wherein the adhesion promotingagent is in a mineral binder composition.
 10. The article ofconstruction of claim 9 wherein the mineral binder is a hydraulic binderselected from the group consisting of cements, aluminous orblast-furnace type, fly ash, calcined shales and pozzolans and whereinthe amount of phosphate monoester, diester or triester is between 0.01%and 50% by dry weight of phosphate monoester, diester or triesterrelative to the total weight of the composition.
 11. The article ofconstruction of claim 10 wherein the amount of phosphate monoester,diester or triester is between 0.02% and 2% by dry weight of thephosphate monoester, diester or triester relative to the total weight ofthe composition.
 12. The article of construction of claim 1 wherein theheat insulating material comprises a component select from the groupconsisting of mineral wools, polystyrene and polyurethane.
 13. Thearticle of construction of claim 12 wherein the heat insulating materialis polystyrene.
 14. The article of construction of claim 13 wherein thepolystyrene is extruded or expanded polystyrene.
 15. The article ofconstruction of claim 1 wherein the mineral building material isselected from the group consisting of masonry, concrete, mineralrenderings, and mortar.
 16. The article of construction of claim 15wherein the mineral building material is a substrate for ceramic tilesor a facade.
 17. The article of construction of claim 1 wherein thearticle of construction serves to interrupt a thermal bridge.
 18. Amethod of preparing an article of construction of claim 1 wherein theadhesion promoter is applied to a surface in the form of a primer. 19.The method of claim 18 wherein the surface is a surface of a heatinsulating material.